Selective layer formation using deposition and removing

ABSTRACT

Methods and systems for selectively depositing dielectric films on a first surface of a substrate relative to a passivation layer previously deposited on a second surface are provided. The methods can include at least one cyclical deposition process used to deposit material on the first surface while the passivation layer is removed, thereby preventing deposition over the passivation layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 16/399,328, filed Apr. 30, 2019, which claims priority to U.S.Provisional Patent Application No. 62/666,039, filed May 2, 2018, thedisclosures of each of which are incorporated herein by reference intheir entireties for all purposes.

BACKGROUND Field

The present disclosure relates generally to the field of semiconductordevice manufacturing and, more particularly, to selective formation oflayers employing deposition and removal of films.

Description of the Related Art

In the semiconductor industry, there is an increasing need for selectiveprocesses. For example, film growth may be desired on one surface butnot on a second, different surface. These two different surfaces cancomprise different materials, for example a metal and a dielectric. Goodselective processes could reduce the number process steps by avoidingmore complicated processes for separate patterning of the depositedmaterial, such as photolithographic masking and patterning, thus savingtime and money.

SUMMARY

In one aspect a method is provided for an atomic layer deposition (ALD)process for selectively forming a dielectric material on a first surfaceof a patterned substrate. The method includes providing a substratecomprising a first surface and a second surface, wherein the secondsurface comprises a passivation layer thereover. The method furtherincludes conducting at least one deposition cycle comprising alternatelyand sequentially contacting the substrate with a first precursor and asecond reactant comprising oxygen. The method further includes whereinthe second reactant reacts with the first precursor to form a dielectricmaterial on the first surface, and wherein the passivation layer isashed by the second reactant during each deposition cycle.

In some embodiments, the method for an ALD process further includeswherein the first surface is a dielectric surface. In some embodiments,the dielectric surface comprises silicon oxide. In some embodiments, thefirst surface comprises a low-k material. In some embodiments, thesecond surface is a metal surface. In some embodiments, the metalsurface comprises at least one of Co, Cu or W. In some embodiments, thedielectric material is an oxide. In some embodiments, the oxide issilicon oxide. In some embodiments, the oxide is a metal oxide.

In some embodiments, the first precursor comprises a metal precursor, asilicon precursor, or mixtures thereof. In some embodiments, the firstprecursor is an alkylaminosilane.

In some embodiments, the passivation layer comprises an organicmaterial. In some embodiments, the passivation layer is selectivelydeposited on the second surface relative to the first surface prior tobeginning the first deposition cycle. In some embodiments, thedeposition cycle is repeated a plurality of times to form an oxide filmof a desired thickness on the dielectric surface. In some embodiments,additional passivation layer is selectively deposited on the passivationlayer between the beginning and end of each deposition cycle.

In some embodiments, the ALD process is a plasma enhanced atomic layerdeposition (PEALD) process. In some embodiments, the at least onedeposition cycle begins with contacting the substrate with the secondreactant before contact with the first precursor. In some embodiments,the at least one deposition cycle further comprises contacting thesubstrate with at least one additional reactant in each cycle. In someembodiments, the second reactant further comprises plasma. In someembodiments, contacting the substrate with the second reactant furthercomprises activating the second reactant with plasma.

In some embodiments, the dielectric material is selectively formed onthe first surface relative to the passivation layer. In someembodiments, the dielectric material is formed on the passivation layerand the dielectric material is removed from the passivation layer withthe ashing of the passivation layer, thereby selectively forming thedielectric material on the first surface.

In another aspect a cyclical deposition process is provided forselectively a forming a material on a surface of a patterned substrate.The method includes providing a substrate comprising a first surface anda second surface, wherein the second surface comprises a passivationlayer thereover. The method further includes conducting at least onedeposition cycle comprising alternately and sequentially contacting thesubstrate with a first precursor and a second reactant. The secondreactant reacts with the first precursor to form the material on thefirst surface, and the passivation layer is etched by the secondreactant during each deposition cycle.

In some embodiments, the process comprises atomic layer deposition(ALD). In some embodiments, the process comprises plasma enhanced ALD(PEALD). In some embodiments, the second reactant comprisesplasma-activated species. In some embodiments, the second reactantcomprises oxygen, the passivation layer comprises an organic layer, andetching comprises ashing. In some embodiments, the passivation layercomprises a polymer.

In some embodiments, deposition is halted before the etching of thepassivation layer exposes the second surface. In some embodiments, themethod includes further depositing additional passivation layer over thesecond surface after halting the deposition and prior to continuing thedeposition.

In another aspect a plasma enhanced atomic layer deposition (PEALD)process is provided for selectively forming an oxide material on a firstdielectric surface of a patterned substrate. The method includesproviding a substrate comprising a first dielectric surface and a secondmetallic surface, wherein the second metallic surface comprises anorganic passivation layer thereover. The method further includesconducting at least one deposition cycle comprising alternately andsequentially contacting the substrate with a first precursor and asecond reactant comprising oxygen and plasma. The second reactant reactswith the first precursor to form an oxide material on the firstdielectric surface, and the organic passivation layer is ashed by thesecond reactant during each deposition cycle.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a flow diagram illustrating a selective deposition processfor depositing a material on a first surface while reducing thethickness of a passivation layer over a second surface.

FIG. 1B is a flow diagram illustrating a selective deposition processfor depositing a material on a first surface while reducing thethickness of a passivation layer selectively deposited over a secondsurface.

FIG. 2 is a graph of some embodiments showing the thickness of apolyimide layer versus the number of cycles of oxidation performed,wherein a passivation ash rate is calculated.

FIG. 3 illustrates the selective deposition of a material on a firstsurface of a substrate by a cyclical deposition process, while thecyclical deposition process removes a passivation layer over a secondsurface.

DETAILED DESCRIPTION

Dielectric films, such as metal oxide or silicon oxide (e.g., SiO)films, have a wide variety of applications, as will be apparent to theskilled artisan, for example in integrated circuit fabrication.According to some embodiments of the present disclosure, variousdielectric films, particularly oxide films, precursors, and methods fordepositing such films are provided.

In some embodiments, a material is formed on a first surface of asubstrate relative to a second surface by a selective depositionprocess. In some embodiments, the material is an oxide material. In someembodiments, a dielectric film is formed selectively using a cyclicaldeposition process on a dielectric surface of a substrate relative to apassivation layer on a metal surface.

For example, FIG. 1A is a flow diagram 100 illustrating a selectivedeposition process of depositing a material on a first surface whilereducing the thickness of a passivation layer over a second surface. Inthe first illustrated block 102 a substrate with a first surface and asecond surface is provided, wherein the second surface comprises apassivation layer thereover. In block 104 the substrate is contactedwith a first reactant, and in block 106 the substrate is contacted witha second reactant. In some embodiments, blocks 104 and 106 are performedalternately and sequentially. In illustrated decision block 108, thesubstrate may be repeatedly exposed to the first and second reactants inblocks 104 and 106 until a material of sufficient thickness is formed.In some embodiments, a sufficiently thick material is formed andtherefore blocks 104 and 106 are not repeated. In some embodiments, asufficiently thick material is not formed and therefore blocks 104 and106 are repeated, and the repetition of blocks 104 and 106 is referredto as a cyclical deposition process. Blocks 104 and 106 need not be inthe same sequence nor identically performed in each repetition. In someembodiments, blocks 104 and 106 are performed consecutively. In someembodiments, blocks 104 and 106 are separated by one or moreintermittent processes. In some embodiments, the repetition of blocks104 and 106 are performed consecutively. In some embodiments, therepetition of blocks 104 and 106 is separated by one or moreintermittent processes. In some embodiments, intermittent processes maybe selected from at least one of excess reactant and byproduct removal(e.g., vacuum and/or inert gas purge), selective deposition of anadditional passivation layer, additional clean up etch, repeatedexposure of the same reactant prior to exposure of another reactant,and/or exposure to an additional reactant in some or all cycles.Intervening removal of excess reactant and byproduct aids in separatingthe supply of different reactants to minimize risk of gas phaseinteraction and limit the deposition reactions to surface reactions.Skilled artisans will appreciate that some interactions with residualgases may be tolerated in order to minimize duration of the interveningremoval (e.g., purge) steps. Avoiding overlap in the supply of reactantsto the reaction space typically reduces gas phase reactionssufficiently, and optimization of flow paths together with interveningpurging can further minimize residual gas interactions. Once a desiredmaterial is thickness is formed, the selective deposition process iscompleted in block 110, where the material is selectively obtained on afirst surface and a passivation layer with a reduced thickness isobtained on the second surface. Reactants can be precursors that leaveone or more elements in the deposited film. In some embodiments, one ormore reactants can serve to chemically reduce, oxidize or getterproducts of the deposited material.

Similar to FIG. 1A, FIG. 1B is an example flow diagram 200 illustratingthe selective deposition of a material on a first surface while reducingthe thickness of a passivation layer, however FIG. 1B includesselectively forming a passivation layer on a second surface. It is to beunderstood that any of the same or similar features or functionsdiscussed with regard to FIG. 1A may also be applied to the same orsimilar features or functions of FIG. 1B. In the first illustrated block202 a passivation layer is selectively formed on a second surface of asubstrate relative to a first surface. In block 204 the substrate iscontacted with a first reactant, and in block 206 the substrate iscontacted with a second reactant. In illustrated decision block 208, asufficiently thick material may be formed and therefore the material isselectively obtained on the first surface with a passivation layer of areduced thickness as shown in block 212. If a sufficiently thickmaterial is not yet formed and if the passivation layer is not at riskof being fully consumed by exposure to the reactants, decision block 210illustrates that the substrate may be repeatedly and alternately exposedto the first and second reactants in blocks 204 and 206. Alternatively,if the passivation layer is at risk of being fully consumed by exposureto the reactants, decision block 210 illustrates that first illustratedblock 202 may be repeated where a passivation layer is selectivelyformed on a second surface of a substrate relative to a first surfacebefore the substrate is exposed to the first and second reactants inblocks 204 and 206.

In some embodiments, the cyclical deposition process is atomic layerdeposition (ALD). In some embodiments, the cyclical deposition processis cyclical chemical vapor deposition (CVD). In some embodiments, thepassivation layer was previously deposited on the second surface (forexample, the metal surface). In some embodiments, the passivation layeris partially removed during the cyclical deposition process. During anALD process, for example, the passivation layer may be slowly removed,such as by etching, during ALD phases. For example, for an organic(e.g., polymer) passivation layer, etching (e.g., ashing) may beaccomplished during deposition phases in which oxidants are supplied,while simultaneously a dielectric film is deposited on the dielectricsurface. In another example, a passivation layer is simultaneouslyremoved while an oxide material is deposited on the dielectric surfaceduring exposure of the substrate to a second reactant in the ALDprocess. The slow etching of the passivation layer may preventdeposition of the dielectric on the passivation layer and on the metal.

In some embodiments, the ALD process may be a plasma enhanced atomiclayer deposition process (PEALD). In some embodiments, plasma power isprovided to generate more reactive species from reactants containingoxygen. In some embodiments, reactant containing oxygen comprises O₂gas, which is subjected to plasma generating power. In some embodiments,the plasma may be generated remotely from the deposition chamber andplasma products supplied to the deposition chamber. In some remoteplasma embodiments, the delivery path optimizes delivery of neutral Ospecies while minimizing ion delivery to the substrate. In someembodiments, the plasma may be generated in situ within the depositionchamber.

In some embodiments, the first surface of the substrate comprises adielectric surface. In some embodiments, the dielectric surface of thesubstrate comprises a silicon oxide (e.g., SiO₂). In some embodiments,the dielectric surface of the substrate comprises a low-k material.

In some embodiments, the second surface comprises a metal surface.Unless otherwise indicated, if a surface is referred to as a metalsurface herein, it may be a metal surface or a metallic surface. In someembodiments the metal or metallic surface may comprise metal, metaloxides, and/or mixtures thereof. In some embodiments the metal ormetallic surface may comprise surface oxidation. In some embodiments themetal or metallic material of the metal or metallic surface iselectrically conductive with or without surface oxidation. In someembodiments metal or a metallic surface comprises one or more transitionmetals. In some embodiments the metal or metallic surface comprises oneor more of Al, Cu, Co, Ni, W, Nb, Fe. In some embodiments the metal ormetallic surface comprises at least one of Co, Cu or W. In someembodiments the metal or metallic surface comprises one or more noblemetals, such as Ru. In some embodiments the metal or metallic surfacecomprises a conductive metal oxide, nitride, carbide, boride, orcombination thereof. For example, the metal or metallic surface maycomprise one or more of RuO_(x), NbC_(x), NbB_(x), NiO_(x), CoO_(x),NbO_(x) and WNC_(x). In some embodiments the substrate may comprise ametal nitride, including, but not limited to TiN and/or TaN. In someembodiments the metal surface may comprise a metal carbide, including,but not limited to TiC and/or TaC. In some embodiments the metal surfacemay comprise a metal chalcogenide, including, but not limited to MoS₂,Sb₂Te₃, and/or GeTe. In some embodiments the metal surface is a TiNsurface. In some embodiments the metal surface is a W surface.

Selectivity

Selectivity can be given as a percentage calculated by [(deposition onfirst surface)-(deposition on second surface)]/(deposition on the firstsurface). Deposition can be measured in any of a variety of ways. Insome embodiments deposition may be given as the measured thickness ofthe deposited material. In some embodiments deposition may be given asthe measured amount of material deposited.

In some embodiments selectivity is greater than about 10%, greater thanabout 50%, greater than about 75%, greater than about 85%, greater thanabout 90%, greater than about 93%, greater than about 95%, greater thanabout 98%, greater than about 99% or even greater than about 99.5%. Inembodiments described herein, the selectivity can change over theduration or thickness of a deposition.

In some embodiments deposition of the dielectric, such as an oxide, onlyoccurs on the first dielectric surface and does not occur on thepassivation layer over the second metal surface. In some embodimentsdeposition on the first surface of the substrate relative to thepassivation layer is at least about 80% selective, which may beselective enough for some particular applications. In some embodimentsthe deposition on the first surface of the substrate relative to thepassivation layer is at least about 50% selective, which may beselective enough for some particular applications. In some embodimentsthe deposition on the first surface of the substrate relative to thepassivation layer is at least about 10% selective, which may beselective enough for some particular applications.

In some embodiments the passivation layer may be selectively formed onthe metal surface prior to selective deposition of the dielectricmaterial on the dielectric surface. For example, in some embodiments, apassivation layer may be blanket deposited on a patterned substrate, andpatterned and etched by traditional processes to leave the passivationlayer selectively where the subsequent deposition is to be avoided, suchas over a metal surface. In other embodiments, a passivation layer maybe selectively deposited on a metal layer. Selective deposition of apassivation layer may be carried out, for example, as described below,and as described in US Patent Publication No. 2017-0352533 A1(application Ser. No. 15/170,769) or US Patent Publication No.2017-0352550 A1 (application Ser. No. 15/486,124), the entire disclosureof each of which is incorporated by reference herein in its entirety.

As noted above, the selective formation of the passivation layer overmetal surfaces need not be 100% selective in order to achieve 100%selectivity. For example, the passivation layer deposition may bepartially selective such that it is formed to be thicker over the metalsurface than over the dielectric surface. A subsequent short, timed etchof the passivation material may be conducted for a duration to exposethe dielectric surface while leaving some passivation layer covering themetal surface.

ALD Process

According to some embodiments, a dielectric film is deposited on a firstsurface of a substrate with an oxygen based ALD process. In someembodiments, the deposited dielectric film may be, for example, siliconoxide (e.g., SiO₂) or other metal oxide that can be grown with a PEALDprocess. In some embodiments, the deposited dielectric film can compriseSiO₂, TiO₂, ZrO₂, HfO₂, Nb₂O₅, Ta₂O₅, WO₃, NiO and combinations thereof.The second surface of the substrate may be covered by a passivationlayer. In some embodiments, the passivation layer is an organic layer.The organic passivation layer may be a polymer, such as polyimide orpolyamide.

In some embodiments, an oxide material film is deposited on a firstsurface of a substrate with an oxygen based ALD process. In someembodiments, the deposited oxide material film may be a conductive oxidefilm. For example, in some embodiments the conductive oxide film is anindium tin oxide (ITO) film. In some embodiments, the deposited oxidematerial film may be a dielectric film, as described herein.

In some embodiments, the passivation layer inhibits oxide material filmand/or dielectric film deposition there. However, in some embodiments,the passivation layer does not inhibit deposition of the oxide materialfilm or dielectric film, that is, the oxide material film or dielectricfilm chemistry may not be selective as between the underlying dielectricsubstrate surface and the passivation layer. This is due to the factthat conditions are selected to ensure some removal of the passivationlayer during the ALD process, thus undercutting and removing anydeposition of the oxide material film or dielectric film over thepassivation layer. As the passivation layer is sacrificial, thepassivation layer is slowly removed (e.g., etched) during one of thecyclical deposition phases. For example, in an ALD sequence, an organic(e.g., polymer) passivation layer may be slowly ashed by an oxidantphase of the ALD sequence, which prevents oxide material film ordielectric film growth on the passivation layer. In another example, inan ALD sequence, a passivation layer is removed during exposure of thesubstrate to a second reactant in the ALD process, which prevents oxidematerial film or dielectric film growth on the passivation layer.Relative to the growth over the passivation layer, the oxide materialfilm or dielectric film is deposited normally (non-selectively, or withlow selectivity) on the dielectric surface. Regardless of whether theoxide material film or dielectric material is deposited normally orselectively on the dielectric surface, slowly etching (e.g., ashing) thesacrificial passivation layer by an oxidant phase of the ALD sequencehas the end effect of selectively forming the oxide material film ordielectric material on the dielectric substrate relative to thepassivation layer. Thus, using the process of FIG. 1A or 1B caneffectively increase selectivity of the formation of the oxide materialfilm or dielectric film.

In some embodiments, before deposition of the oxide material film ordielectric film is performed but after the passivation layer is formed,any passivation layer remaining on the dielectric surface can be removedwith a plasma pretreatment with suitable parameters. In someembodiments, rather than a separate process to remove any passivationmaterial from over the dielectric surface, any passivation layerremaining on the dielectric surface is removed by initial phases of theALD process, including oxidation phase, or by simply conducting theoxidation phase of the ALD process before initiating the full ALDprocess wherein after the thinner passivation layer on dielectric iscompletely ashed the oxide material film or dielectric film depositionprocess begins. Thus, the ALD sequence may start with the secondreactant, including oxidant, to serve for a short timed etch ofundesired passivation material from the first surface, without removalof all the passivation material from the second surface, beforeselective deposition on the first surface.

In some embodiments, the oxidation phase of the ALD process is a plasmaprocess in a PEALD sequence. In some embodiments, the plasma is oxygenbased. For example, the plasma may be generated in O₂ gas or a mixtureof O₂ and a noble gas, such as Ar. In some embodiments the plasma may begenerated in a gas comprising oxygen, or may otherwise comprise excitedoxygen species. In some embodiments, the oxidation phase of the ALDprocess is a non-plasma oxidation process (e.g., H₂O or O₃).

In some embodiments plasma, for example oxygen containing plasma, may begenerated by applying RF power of from about 10 W to about 2000 W, fromabout 50 W to about 1000 W, from about 100 W to about 500 W, from about30 W to 100 W, or about 100 W in some embodiments. In some embodimentsthe RF power density may be from about 0.02 W/cm² to about 2.0 W/cm², orfrom about 0.05 W/cm² to about 1.5 W/cm². The RF power may be applied toa reactant that flows during the plasma contacting time, that flowscontinuously through the reaction chamber, and/or that flows through aremote plasma generator. Thus in some embodiments the plasma isgenerated in situ, while in other embodiments the plasma is generatedremotely. In some embodiments a showerhead reactor is utilized andplasma is generated in situ between a susceptor (on top of which thesubstrate is located) and a showerhead plate. In some embodiments thegap between the susceptor and showerhead plate is from about 0.1 cm toabout 20 cm, from about 0.5 cm to about 5 cm, or from about 0.8 cm toabout 3.0 cm.

The thickness of the oxide film that can be formed on dielectric surfacebefore the passivation layer is completely removed depends on thepassivation layer initial thickness, ash rate of the passivation layer,and the growth rate of the oxide deposition process. For example, FIG. 2demonstrates that with an ash rate of ˜0.2 Å/cycle, a 20 nm sacrificialpolyimide layer on a metal surface, and a growth per cycle (GPC) of 1Å/cycle, 50 nm of SiO₂ may be deposited on a dielectric surface byapplying 500 cycles of the oxygen based PEALD process. FIG. 2 shows theash rate of polyimide when exposed to oxidant phases in which argon issupplied at 700 sccm, O₂ is supplied at 100 sccm, pressure is kept at 2Torr, plasma power is set to 100 W, substrate temperature is maintainedat 100° C., and each oxidant phase includes 1 second of O₂ plasma and 1second of purge. The PEALD would include one phase of the above oxidantphase alternated with supply of a silicon precursor and purge, where thesilicon precursor is selected for adsorption on the dielectric orgrowing silicon oxide film and to react with the oxidant phases to formsilicon oxide. In other embodiments, oxidant phases can be alternatedwith a supply of one or more metal precursor phase(s) and attendantpurge phase(s), where the metal precursor is selected to adsorb on thedielectric surface or the growing metal oxide film and to react to withthe oxidant phases to form the desired oxide.

In some embodiments, optimization of the etch rate of the sacrificialpassivation layer can be tuned so that growth of the oxide material filmor dielectric film does not result in net deposition on the passivationlayer during the ALD process. In some embodiments, the incubation timefor deposition on the passivation layer is sufficiently long enough thata desired oxide layer thickness is deposited on the dielectric surface.In some embodiments a thick enough passivation layer is formed over themetal surface such that a sufficiently thick oxide film may be depositedover the dielectric surface using the ALD process without furtherdepositing another passivation film layer, i.e., without fully consumingthe initial passivation layer.

In some embodiments, a selective passivation layer deposition and theselective ALD process are performed in an iterative manner, for examplesuch using the process described in FIG. 1B. This iterative process mayenable the thickness of the passivation layer to be replenished afterthe ALD process is performed, therefore allowing subsequent ALDprocesses to be performed. For example, if the passivation layer isashed away in 100 cycles or if the incubation on passivation layer is100 cycles before the deposited oxide begins to form on the passivationlayer faster than it can be removed by undercutting, 90 cycles of afirst ALD process may be performed to selectively deposit the oxide onthe dielectric surface, deposition of a subsequent passivation layerover the previous passivation layer may be performed, and a second 90cycles of the ALD process may be performed. In some embodiments, thisiterative process may be repeated as many times as desired to obtain adesired oxide layer thickness on the dielectric surface. A person ofordinary skill in the art would appreciate that the number of iterativeprocesses necessary would vary depending on a number of factors such as,for example, the thickness of the deposited oxide desired, the thicknessof the passivation layer, and the ash rate or incubation period of thepassivation layer.

In some embodiments, the PEALD deposition may be carried out essentiallyas described above. In other embodiments, the substrate is alternatelyand sequentially contacted with a first reactant comprising elements tobe included in the deposited material, such as a metal or silicon, and asecond reactant comprising oxygen, and a second plasma reactant. In someembodiments the second plasma reactant does not comprise oxygen species.In some embodiments no reactants comprising oxygen species are usedother than the second reactant. The plasma and precursors (i.e. thefirst and second reactants) may be provided in pulses separated by aremoval process (e.g., purge) in which excess reactant and reactionbyproducts, if any, are removed from the reaction space. In someembodiments, a PEALD deposition process begins with the plasma pulsefollowed by the precursors, and the reaction sequence, or depositioncycle, may be repeated a desired number of times (A):A×(plasma pulse/purge/precursors/purge)

In some embodiments the deposition cycle begins with the non-plasmaprecursors, which is then followed by the plasma pulse.

According to some embodiments, PEALD processes utilized may be anysuitable oxygen based plasma processes. In some embodiments, thedeposited dielectric film is an oxide film. In some embodiments, thedeposited dielectric film is a metal oxide film. In some embodiments,the deposited dielectric film may be selected from the group consistingof SiO₂, TiO₂, ZrO₂, HfO₂, Nb₂O₅, Ta₂O₅, WO₃ and NiO. In someembodiments, the deposited dielectric film is silicon oxide. In someembodiments, an oxide precursor is an alkylaminosilane, which is used todeposit silicon oxide films.

In some embodiments, an oxide film is selectively formed on a firstdielectric surface of a substrate relative to a second, different metalor metallic surface of the substrate by an oxygen-based PEALD process.For example, silicon oxide may be selectively deposited by oxygen-basedPEALD on a low-k dielectric surface (e.g., silicon oxide-based surface)relative to a metal surface.

FIG. 3 shows a schematic of some embodiments, wherein a substrate 302comprises a first surface of a first structure 304 (for example, adielectric surface of a dielectric layer) and a second surface of asecond structure 306 that has a different material composition (forexample, a metal surface of a metal layer, such as a cobalt, copper ortungsten surface) further comprising an initial passivation layer 308Ahaving a first thickness (for example, 20 nm of a polyimide organiclayer), in which a material 312 is selectively deposited on the firstsurface relative to the second surface (due to selectively relative tothe overlying initial passivation layer 308A). In some embodiments theselectively deposited material 312 is an oxide material. In someembodiments, the oxide material is a dielectric material. In examplesdescribed herein, the dielectric oxide is a film of silicon oxide. Ascan be seen in FIG. 3, after one or more cycles of a selectivedeposition process 310 (for example, 500 cycles of an oxygen based PEALDsilicon oxide deposition process), the material 312 (for example, 50 nmof SiO) is deposited over the first surface of the first structure 304and the remaining passivation layer 308B has decreased to a secondthickness (for example, 10 nm of a polyimide organic layer). In someembodiments, the selective deposition process halts before all of theinitial passivation layer is removed. In some embodiments, after theselective deposition process is completed, the reduced thickness of theremaining passivation layer 308B may be subsequently removed (forexample, by ashing) without deposition to expose the second surface ofthe second structure 306.

In some embodiments, the PEALD process disclosed may accomplishselective formation of silicon oxide or other oxides on dielectricsurfaces. In some embodiments, the PEALD process disclosed mayaccomplish a reduction in the number of steps for forming desiredpatterns in various device manufacturing process flows, relative toconvention patterning processes.

It will be understood by those of skill in the art that numerous andvarious modifications can be made without departing from the spirit ofthe present invention. The described features, structures,characteristics and precursors can be combined in any suitable manner.Therefore, it should be clearly understood that the forms of the presentinvention are illustrative only and are not intended to limit the scopeof the present invention. All modifications and changes are intended tofall within the scope of the invention, as defined by the appendedclaims.

What is claimed is:
 1. A method of selectively forming a dielectricmaterial on a first surface of a substrate, the method comprising:providing a substrate comprising a first surface and a second surface,wherein the second surface comprises a passivation layer thereover;conducting a cyclical deposition process that comprises a plurality ofdeposition cycles, wherein at least one deposition cycle of thedeposition cycles comprises separately contacting the substrate with aprecursor and a reactant comprising oxygen; wherein the reactant reactswith the precursor on the first surface to form a dielectric material onthe first surface; and wherein passivation material of the passivationlayer is ashed by the reactant during the at least one deposition cycle,such that a result of the cyclical deposition process is to selectivelyform the dielectric material on the first surface.
 2. The method ofclaim 1, further comprising depositing additional passivation materialover the passivation layer between an end of the one deposition cycle ofthe cyclical deposition process and a beginning of a subsequentdeposition cycle of the cyclical deposition process.
 3. The method ofclaim 1, wherein the cyclical deposition process is halted before theashing of the passivation layer exposes the second surface.
 4. Themethod of claim 1, wherein the passivation layer is ashed in each of thedeposition cycles of the cyclical deposition process that includecontacting the substrate with the reactant.
 5. The method of claim 1,further comprising selectively depositing the passivation layer on thesecond surface relative to the first surface prior to beginning a firstdeposition cycle of the at least one deposition cycle.
 6. The method ofclaim 1, wherein the at least one deposition cycle is repeated aplurality of times to form an oxide film of a desired thickness on thefirst surface.
 7. The method of claim 6, further comprising selectivelydepositing additional passivation material over the second surfacebetween a beginning and an end of the cyclical deposition process. 8.The method of claim 1, wherein said contacting the substrate with thereactant comprises activating the reactant with plasma.
 9. The method ofclaim 1, wherein the first surface is a dielectric surface.
 10. Themethod of claim 1, wherein the first surface comprises silicon oxide.11. The method of claim 1, wherein the second surface is a metalsurface.
 12. The method of claim 1, wherein the passivation layercomprises an organic material.
 13. The method of claim 1, wherein the atleast one deposition cycle begins with contacting the substrate with thereactant before contacting the substrate with the precursor.
 14. Themethod of claim 1, wherein the cyclical deposition process is an atomiclayer deposition process.
 15. A method for selectively forming amaterial on a surface of a patterned substrate, the method comprising:providing a substrate comprising a first surface and a second surface,wherein the second surface comprises a passivation layer thereover;conducting deposition cycles, wherein at least one of the depositioncycles comprises separately contacting the substrate with a precursorand a reactant, wherein the reactant reacts with the precursor on thefirst surface to form the material on the first surface, wherein thepassivation layer is etched by the reactant while reacting with theprecursor during the at least one of the deposition cycles, such thatthe deposition cycles selectively form the material on the firstsurface; and depositing passivation material over the second surfacebetween a first deposition cycle of the deposition cycles and a lastdeposition cycle of the deposition cycles.
 16. The method of claim 15,wherein the reactant comprises a plasma-activated species.
 17. Themethod of claim 15, wherein the reactant comprises oxygen, thepassivation layer comprises an organic layer, and etching comprisesashing.
 18. The method of claim 17, wherein the material is formed onthe passivation layer, and wherein the material on the passivation layeris removed by ashing the passivation layer.
 19. A plasma enhanced methodfor selectively forming an oxide material on a dielectric surface of asubstrate, the plasma enhanced method comprising: providing a substratecomprising a dielectric surface and a metallic surface, wherein themetallic surface comprises a passivation layer thereover; and conductingdeposition cycles, at least one deposition cycle of the depositioncycles comprising separately contacting the substrate with a precursorand a reactant, wherein the reactant comprises oxygen and plasma;wherein the reactant reacts with the precursor on the dielectric surfaceto form an oxide material on the dielectric surface; and wherein thepassivation layer is ashed by the reactant during the at least onedeposition cycle, and wherein the oxide material is selectively formedon the dielectric surface by the deposition cycles.
 20. The plasmaenhanced method of claim 19, further comprising depositing passivationmaterial over the metallic surface between a first deposition cycle anda last deposition cycle.